WO2013006867A1 - Procédés et appareil pour former une couche de catalyseur ultramince pour photoélectrode - Google Patents

Procédés et appareil pour former une couche de catalyseur ultramince pour photoélectrode Download PDF

Info

Publication number
WO2013006867A1
WO2013006867A1 PCT/US2012/045988 US2012045988W WO2013006867A1 WO 2013006867 A1 WO2013006867 A1 WO 2013006867A1 US 2012045988 W US2012045988 W US 2012045988W WO 2013006867 A1 WO2013006867 A1 WO 2013006867A1
Authority
WO
WIPO (PCT)
Prior art keywords
semiconductor
catalyst layer
photoelectrode
potential
less
Prior art date
Application number
PCT/US2012/045988
Other languages
English (en)
Inventor
Kimin JUN
Joseph Jacobson
Original Assignee
Massachussetts Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Massachussetts Institute Of Technology filed Critical Massachussetts Institute Of Technology
Publication of WO2013006867A1 publication Critical patent/WO2013006867A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates generally to photoelectrochemical cells.
  • Silicon with its good balance between low cost and narrow band gap matched to the visible solar spectrum, is widely used for photovoltaic applications.
  • silicon has been a poor choice for use in a water-splitting anode, due to silicon's lack of catalytic functionality at the silicon- water interface and its high valence band edge position relative to the anode's oxygen evolution potential (“OEP").
  • high photocurrents are generated by photoanodes comprised of very thin iron-oxide films atop a silicon layer at high pH environment. Silicon plays the role of a primary light absorption layer while the iron-oxide serves as a catalyst.
  • a sufficiently thin catalytic film allows for the silicon band structure to be present at the semiconductor-water interface while still providing for a catalytic water splitting surface. This arrangement allows for the production of particularly high photocurrents at the photoanode.
  • a photoelectrode is a device which absorbs light, generates photocarriers and transports these carriers to ionic chemical species to induce chemical reactions. Therefore, high performance in photocarrier generation is desirable.
  • the generated photocarriers must be consumed by chemical redox reactions.
  • a representative example is water oxidation reaction. Unless the barrier is lowered, carrier transport cannot happen. For this reason, efficient catalysis capability is also desirable in photoelectrode operation.
  • the energy band structure of semiconductor body (light absorption layer) is not distorted by the catalyst layer since band bending of semiconductor layer plays a key role of carrier transport to the surface.
  • the catalyst material If the catalyst is metallic, the space charge region in light absorption layer is governed by semiconductor-metal junction, rather than semiconductor-electrolyte junction. Then, there are two active junctions, semiconductor-metal and metal-electrolyte, which are inter-dependent by metal choice. This increases the complexity and makes it hard to find the optimal metallic catalyst.
  • the catalyst comprises a very thin semiconductor or semiconductor-like insulator. This enables single junction, light absorption layer-electrolyte, since the effect of catalyst can be made negligibly small in junction formation.
  • Second is the catalyst thickness. If the catalyst layer is thick, carriers from light absorption layer cannot be effectively transported to the electrolyte interface due to insulating barrier or recombination junction. Then, unless the catalyst is simultaneously a good photovoltaic semiconductor, the overall current is stagnated by the poor photovoltaic performance. To solve this problem, in exemplary implementations of this invention, the catalyst layer is so thin that the catalyst's contribution to the energy band structure at the junction is minimal.
  • a very thin semiconducting catalyst is deposited on a light absorber, allowing the two functions to be separated.
  • a very affordable materials pair may be used, instead of expensive and exotic materials.
  • Figure 1 is a diagram that shows a cross-sectional view of a photoelectrode, including a nanowire array.
  • Figure 2 is a diagram that shows a cross-sectional view of a photoelectrode that is partially encapsulated in epoxy.
  • Figure 3 is a diagram that shows a cross-sectional view of two half- cells, one of which is a photoanode and the other of which is a photocathode.
  • Figure 4 is a chart showing flat band potential vs. catalyst film thickness (the thickness being expressed as a function of duration of chemical vapor deposition of the film).
  • Figure 5 is a chart showing current density at different thicknesses of catalyst film.
  • Figures 6A and 6B are diagrams showing approximate energy band models relating to a photoanode/electrolyte junction.
  • a photoelectrode includes both (1) a light absorbing semiconductor for photocarrier generation and (2) a catalyst layer for altering the rate of an electrochemical reaction in an electrolyte adjacent to the catalyst layer.
  • the light-absorbing semiconductor and the catalyst are comprised (at least primarily) of different materials.
  • the catalyst layer covers a portion of the light absorbing
  • the catalyst layer is positioned between that portion of the light absorber and the electrolyte.
  • the catalyst layer is "ultrathin".
  • the catalyst layer may be so thin that the energy band structure of the light-absorbing semiconductor (rather than the energy band structure of the catalyst layer) predominates at the electrode /electrolyte junction.
  • the thickness of the catalyst layer may be less than 60% of the minority carrier diffusion distance of the catalyst layer.
  • the catalyst layer may be so thin that the flat band potential of the photoelectrode with the catalyst film present differs by less than 20% from the flat band potential of photoelectrode with the catalyst film is removed.
  • the photoelectrode may be either a photoanode or a photocathode. If the photoelectrode is a photoanode, then the photoanode may be adapted to have an oxygen evolution potential (“OEP") that is more than the potential of the valance band edge of the semiconductor and less than the potential of the Fermi level of the semiconductor, the absolute difference between the OEP and the potential of the valence band edge being greater than zero and less than or equal to 0.2V.
  • OEP oxygen evolution potential
  • the photocathode may be adapted to have an reverse hydrogen evolution (“RHE") potential that is less than the potential of the conduction band edge of the semiconductor and more than the potential of the Fermi level of the semiconductor, the absolute value of the difference between the RHE potential and the potential of the conduction band edge being greater than zero and less than or equal to 0.2V.
  • RHE reverse hydrogen evolution
  • the photoelectrode is a photoanode
  • the interior of the photoanode may be doped with an n-type dopant, and an exterior region of the light- absorbing semiconductor (that is not covered by the catalyst layer) may be n+ doped.
  • the interior of the light absorbing semiconductor may be an n-type material doped with phosphorus, the front side of that semiconductor may be covered by the catalyst layer, and the back side of that semiconductor may be n+ doped with phosphorous.
  • the interior of the photocathode may be doped with a p-type dopant, and an exterior region of the light- absorbing semiconductor (that is not covered by the catalyst layer) may be p+ doped.
  • the interior of the light absorbing semiconductor may be a p-type material doped with boron, the front side of that semiconductor may be covered by the catalyst layer, and the back side of that semiconductor may be p+ doped with boron.
  • At least a portion of the photoelectrode may comprise an array of nanowires or nanotubes.
  • the nanowires or nanotubes may be of any shape, including bent or branching.
  • the nanowires or nanotubes may comprise the light-absorbing semiconductor covered at least in part by the catalyst layer.
  • the light-absorbing semiconductor primarily comprises n-type silicon doped with phosphorus
  • the catalyst layer primarily comprises iron oxide
  • the thickness of the catalyst layer is equal to or less than 10 nm
  • the electrolyte comprises an electrolytic solution with a pH higher than or equal to 10
  • the catalyst layer is on a side of the light-absorbing semiconductor
  • a shallow layer of n+-doped silicon doped with phosphorous is on an other side of the light-absorbing semiconductor.
  • FIG. 1 is a diagram that shows an exemplary embodiment of this invention.
  • a photoelectrode 101 includes both (a) a light absorbing semiconductor 103 for photocarrier generation and (b) a catalyst layer 105 for altering the rate of an electrochemical reaction in an electrolyte adjacent to the catalyst layer.
  • the thickness of some of the layers in Figure 1 is exaggerated for clarity of presentation.
  • the light-absorbing semiconductor 103 may primarily comprise silicon, or another material.
  • the light-absorber 103 may primarily comprise amorphous silicon or cuprous oxide.
  • the light-absorbing semiconductor 103 may primarily comprise a material with a valance band edge equal to 1.23 - 1.25 V vs. RHE.
  • the catalyst layer 105 may itself be semiconducting or nearly insulating.
  • the catalyst 105 may comprise iron oxide, nickel oxide, nickel borate, cobalt oxide, iridium oxide, or another compound that includes cobalt, nickel or iridium.
  • the catalyst 105 has a low doping density.
  • the catalyst layer 105 is positioned between the light-absorbing semiconductor 103 and an electrolyte.
  • the photoelectrode includes an array of nanostructures, such as nanostructure 107.
  • the nanostructures may comprise nanowires or nanotubes.
  • the nanostructures e.g., 107) are covered at least in part by the catalyst layer 105.
  • the interior of the light-absorbing semiconductor is lightly doped (with an n-type material such as phosphorous if the photoelectrode is a photoanode, or with a p-type material such as boron if the photoelectrode is a photocathode).
  • An exterior region 109 of the light-absorbing semiconductor (that is not covered by catalyst layer 105) is heavily doped (n+ doping or p+-doping if the photoelectrode is a photoanode or photocathode, respectively).
  • this exterior, heavily doped region 109 may comprise the "back side" of the photolectrode, if the catalyst layer is on the "front side" of the photoelectrode.
  • a photoanode was fabricated as follows: Silicon electrodes were made of 4" n-type phosphorous-doped silicon wafers (resistivity 5-25 ⁇ -cm, thickness 500-550 ⁇ , (100) orientation) This wafer was diced into l x l cm 2 pieces that were cleaned in organic solvents and 1: 10 hydrofluoric acid (HF, 49 % wt): deionized water solution before chemical vapor deposition (CVD).
  • the CVD setup comprises two bubblers and three mass flow controllers (MFC, 1479A, MKS Instruments ®).
  • iron pentacarbonyl Fe(CO) 5 , Sigma-Aldrich®
  • titanium isopropoxide Ti[OCH(CH 3 ) 2 ] 4 , Sigma-Aldrich ⁇
  • Iron pentacarbonyl was chilled in a cold water bath at 5 °C, and the titanium isopropoxide was maintained at room temperature (20°C).
  • 10 standard cubic centimeters per minute (seem) argon and 250 seem oxygen were fed into iron and titanium precursors respectively. These two precursors and extra oxygen (350 seem) were mixed and fed into a glass funnel (an enlarging adapter, 14/20 to 24/40).
  • the silicon substrate was placed on a heated surface (-173 °C), and the glass funnel was placed with 1 mm clearance from the bottom. Film thickness was controlled by deposition time.
  • the substrate backside was cleaned for a short time (1 minute) by 1 : 10 HF:deioninzed water before metal deposition.
  • a thermal evaporator 7 nm aluminum and 50 nm silver were deposited in order.
  • a silver wire with 0.5 mm diameter was attached to the metal contact by silver paint (silver in MIBK, Ted Pella, Inc.) and dried for 30 minutes.
  • the silver wire was insulated using Teflon® tubing, and the backside was encapsulated with epoxy on slide glass. The epoxy was cured for more than 2 hours at 70 °C.
  • the device was cleaned by ozone (Aqua-6 ozone generator, A2Z Ozone, Inc.) for 10 minutes.
  • FIG 2 is a diagram that shows a cross-sectional view of a photoelectrode 200 that is partially encapsulated in epoxy.
  • the photoelectrode 200 comprises layers of iron oxide 201, silicon 203, aluminum 205, and silver 207.
  • the silver 207 is attached to a silver wire 213 that is insulated with
  • Epoxy 209 encapsulates the back and side of the photoelectrode in order to electrically insulate the photoelectrode from the electrolyte.
  • the epoxy 209 does not, however, cover the top of the iron oxide layer 201 , so the iron oxide catalyst 201 directly contacts the electrolyte.
  • the epoxy is attached to a layer of glass 211.
  • FIG. 3 is a diagram that shows a cross-sectional view of two half- cells of photoelectrodes, one of which is a photoanode 301 and the other of which is a photocathode 303.
  • the photoanode 301 comprises n-type silicon 304 with an iron oxide catalyst layer 305.
  • the photoanode 301 generates photocarriers.
  • the iron oxide catalyst layer 305 increases the reaction rate of a water-splitting (oxygen evolution) reaction 307 in electrolyte solution that is adjacent to the catalyst.
  • the photocathode 303 comprises a p-type semiconductor 309 and a hydrogen evolution catalyst 311.
  • Catalyst 311 increases the reaction rate of a hydrogen evolution reaction 313 in electrolyte solution that is adjacent to catalyst 311.
  • the photocathode 303 In response to light 314 with a wavelength less than ⁇ 0 , the photocathode 303 generates photocarriers.
  • ⁇ 0 means the wavelength of light at which the photon energy of light is equal to the bandgap energy of the p-type semiconductor 309 in the photocathode 303.
  • Figure 4 is a chart showing measured flat band potential vs. catalyst film thickness (the thickness being expressed as a function of duration of chemical vapor deposition of the film).
  • photoanodes were made of n + back doped silicon substrates to minimize the effect of Schottky space charge region.
  • Iron-oxide catalyst films were prepared for various thickness of 0, 6, 10 and 20 nm,(corresponding to 0, 3, 5 and 10 minutes deposition) and three different pH electrolytes (10, 12 and 13.8) were also prepared. Fluctuation voltage was set to 5 mV rms. Potential scan started from 0.5 V vs. Ag/AgCl to cathodic direction.. (End points vary on samples, typically -0.8 ⁇ -0.9 V vs.
  • Figure 5 is a chart showing measured current density at different thicknesses of catalyst film, in a prototype of this invention. The thickness is expressed as a function of duration of chemical vapor deposition of the film.
  • Figures 6A and 6B are diagrams showing approximate energy band models relating to a photoanode/electrolyte junction, in a prototype of this invention.
  • the photoanode includes (a) a light-absorbing semiconductor that comprises n-type silicon and (b) an ultrathin iron oxide catalyst layer. More particularly, Figure 6A shows approximate energy band levels for the junction immediately after the photoanode is immersed in the electrolyte.
  • Figure 6B shows approximate energy band levels for the junction after the photoanode has been immersed in the electrolyte sufficiently long for the junction to be in thermal equilibrium. When the electrode- electrolyte junction is in thermal equilibrium, the Fermi level of silicon and the OEP (oxygen evolution potential) become closely aligned, as shown in Figure 6B.
  • OEP locates higher (more cathodic) than the silicon valence band edge.
  • oxygen evolution reaction may happen in silicon and electrolyte junction.
  • the lack of catalytic functionality of silicon prohibits the procession of the reaction.
  • a proper catalyst like iron-oxide is introduced, the charge carriers can pass through the junction.
  • the space charge region of the iron oxide/electrolyte junction can be calculated using Poisson's equation.
  • the Fermi level of the iron-oxide can be estimated from known flat band potential.(-0.6 V vs. standard calomel electrode(SCE)). Then, the surface barrier (difference between iron-oxide Fermi level and OEP) is about 0.7 V. If iron- oxide carrier concentration is assumed to be about 10 16 cm "3 with a dielectric constant about 60, then the space charge region thickness of the iron-oxide/electrolyte junction may be calculated to be about 680 nm.
  • the iron-oxide has much lower carrier concentration, which means even thicker space charge region. If the iron oxide is sufficiently thin (e.g., less than 10 nm), then the space charge region is much thicker than iron-oxide physical thickness. Therefore, the potential drop by iron-oxide is negligible, and most of the space charge region may occur in the silicon semiconductor instead. This induces steep upward bending in silicon energy band structure, providing potential gain as indicated in figure 6B.
  • Thin iron-oxide film was deposited on silicon substrate by low temperature atmospheric pressure CVD to catalyze oxygen evolution reaction.
  • iron-oxide film was sufficiently thin, around 10 nm or less, otherwise nonresponsive silicon photoanode showed a high photocurrent.
  • Parametric studies revealed that the photoresponses become effective when (1) iron-oxide film is thin, (2) titanium content is high and (3) operation pH is high.
  • the photocarriers are generated by silicon while the role of iron-oxide is limited to catalyst.
  • the catalytic functionality of standalone iron-oxide is fairly good, but not exceptionally outstanding. However, the
  • silicon photoanodes have not been successful due to the lack of catalysis and the energy band mismatch.
  • silicon is successfully used for a photoanode with the help of appropriate catalyst and pH control.
  • Silicon has ideal band edge alignment in certain operational conditions (high pH electrolyte, ultrathin iron oxide catalyst layer, n-type silicon) since oxygen evolution potential is closely aligned with valence band edge. Also, a semiconducting catalyst (iron-oxide) plays an effective catalytic function.
  • n-type silicon is the primary light absorber.
  • An ultrathin iron oxide (a Fe203) catalyst film interposed between the silicon and a high pH electrolyte solution increases the rate of the water- splitting reaction.
  • a-Fe203 is a semiconductor
  • the -10 nm thickness of the iron oxide layers is thinner than the typical nondegenerate semiconductor space-charge region. Since there is no metallic barrier between electrolyte and silicon, most of the space-charge region likely appears within the silicon. Thus, thermal equilibrium induces strong upward bending of silicon energy band because the silicon flat band potential is negative (cathodic) with respect to OEP. This built-in potential, along with a good catalytic performance of iron-oxide, appears to be a reason for high photocurrent in the silicon/iron oxide photoanode.
  • Substrate preparation n-type silicon(( 100) direction, 10-20 ohm-cm) is thoroughly cleaned by organic solvent and HF solution.
  • Back doping for ohmic contact The backside of the silicon is doped to form shallow n + layer to make ohmic contact with metal electrode.
  • spin-on doping was used. Spin-on dopant was coated on the backside of the silicon, and annealed in the tube furnace. Afterward, HF solution was used to etch away the spin-on dopant.
  • Iron-oxide thin film Through atmospheric pressure chemical vapor deposition (CVD), iron-oxide thin film was deposited on the front side of the silicon. The silicon was placed on heating surface, and volatile gas vapor, iron pentacarbonyl (iron-oxide precursor) and titanium isopropoxide(titanium dopant), was fed around this silicon surface. The film thickness is very thin. In this prototype, it is less than 10 nm.
  • Metal contact After CVD, metal contact was made on the silicon backside where n + doping was made. In the embodiment, aluminum layer was deposited first followed by silver deposition.(Silver prevents oxidation during air exposure. Under well controlled fabrication environment, silver can be omitted.) Then, a copper wire was attached to this metal contact.
  • iron-oxide film thickness is controlled by film deposition time whose deposition rate was 2 nm/minute.
  • OEP oxygen evolution potential
  • a parenthesis is simply to make text easier to read, by indicating a grouping of words.
  • a parenthesis does not mean that the parenthetical material is optional or can be ignored.
  • RHE reverse hydrogen electrode
  • Two values differ by a certain percent, if equals that certain percent, where x is the larger of the two values and ⁇ is the smaller of the two values.
  • the material used in the light-absorbing semiconductor is not limited to single crystal silicon.
  • a silicon photoanode produces high photocurrent due to the large built-in potential in semiconductor to liquid junction (under the conditions described with respect to Figure 6B). This comes from the close alignment of the semiconductor valence band and oxygen evolution potential. Therefore, other semiconductors with valence band near 1.23 V vs. RHE would be appropriate (e.g. with a valence band equal to
  • amorphous silicon(a-Si) and cuprous oxide(Cu20) may be used for the light-absorbing semiconductor.
  • This invention is not limited to high pH electrolyte solutions. It may be employed with either basic or acidic electrolyte solutions.
  • This invention is not limited to any particular method of depositing the catalyst layer.
  • any method of vacuum deposition may be employed, such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) (including low pressure chemical vapor deposition, and plasma enhanced CVD).
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the particles being deposited may come, for example, from sputtering.
  • This invention is not limited to using vertical wire arrays (if a wire array is used at all).
  • particle decoration or array configurations may be used to enhance light harvesting capability.
  • wire length adjustment or light incidence angle modification may be used for better silicon efficiency.
  • a roughened surface (e.g., with random bumps) may be used, instead of a wire array.
  • etch-resistive crystal surface like Si(l 11) may be used, which may extend the life time by about 2 ⁇ 3 orders of magnitude (as compared to Si(100) substrate.
  • an active protection layer for the silicon surface may be used.
  • surface alkylation may increase stability of the silicon surface.
  • surface treatment like methylation or hydrophobic coating of the bottom area could elongate the lifetime.
  • the iron-oxide film may experience a gradual detachment from the host surface. This detachment may be mitigated by decreasing current density per iron oxide film area. To compensate for the decreased current density, the surface area can be increased by a corrugated film surface, such as a dendrite structure. 51
  • the film may be strengthened by using sintering, annealing or adding atomic components.
  • adhesion is increased by promoting interlayer between silicon and iron- oxide.
  • a photoanode works on half cell reaction. Since the band gap of silicon is 1.12 eV, which is smaller than water redox potential difference (1.23 V), potential compensation is needed for cathode reaction. This can be achieved with the architecture shown in Figure 3. A photocell or photocathode is stacked with this silicon/iron oxide photoanode and the energy bands of this entire cell straddle the water redox potential. In this architecture, the cathode electrode preferably has band alignment for hydrogen evolution. This stacked photodevice can be located either upstream or downstream of the silicon/iron oxide photoanode. Because the silicon/iron oxide photoanode uses a narrow band gap material (silicon), it is preferable to install the wide band gap cathode stack upstream of the silicon/iron oxide photoanode.
  • This invention may be implemented as a photoelectrode that includes a semiconductor for photocarrier generation and a catalyst layer for altering the rate of an electrochemical reaction in an electrolyte adjacent to the catalyst layer, wherein: (a) the semiconductor primarily comprises a first material and the catalyst layer primarily comprises a second material, the first material being different than the second material, (b) the catalyst layer covers a portion of the semiconductor's surface, (c) the thickness of the catalyst layer is less than 60% of the minority carrier diffusion distance of the catalyst layer, (d) the photoelectrode is either a photoanode or a photocathode, (e) if the photoelectrode is a photoanode, the photoanode is adapted to have an OEP that is more than the potential of the valance band edge of the semiconductor and less than the potential of the Fermi level of the semiconductor, the absolute value of the difference between the OEP and the potential of the valence band edge being greater than zero and less than or equal to 0.2 V,
  • the absolute value of the difference between the RHE potential and the potential of the conduction band edge being greater than zero and less than or equal to 0.2V.
  • the semiconductor may primarily comprise silicon and the catalyst layer may primarily comprise iron oxide; (2) the catalyst layer may comprise iron oxide and the thickness of the catalyst layer may be less than 12 nm; (3) at least a portion of the semiconductor may comprise an array of nano wires or nanotubes that is covered at least in part by the catalyst layer; (4) the photoelectrode may be a photoanode, the interior of the semiconductor may be doped with a first n-type dopant at a first dopant concentration, and an exterior region of the semiconductor that is not covered by the catalyst layer may be doped with a second n-type dopant at a second dopant concentration, the second dopant concentration being greater than the first dopant concentration; (5) the first n-type dopant and second n-type dopant may both comprise phosphorous; (6) the photoelectrode may be a photocathode, the interior of the semiconductor may be doped with a first p-type dopant at a first dopant concentration, and an
  • This invention may be implemented as a photoelectrochemical cell, wherein: (a) the photoectrochemical cell includes a photoelectrode, (b) the photoelectrode includes a semiconductor for photocarrier generation and an catalyst layer for altering the rate of an electrochemical reaction in an electrolyte adjacent to the catalyst layer, (c) the semiconductor primarily comprises a first material and the catalyst layer primarily comprises a second material, the first material being different than the second material, (d) the catalyst layer covers a portion of the semiconductor's surface, (e) the thickness of the catalyst layer is less than 60% of the minority carrier diffusion distance of the catalyst layer, (f) the photoelectrode is either a photoanode or a photocathode, (g) if the photoelectrode is a photoanode, the photoanode is adapted to have an OEP that is more than the potential of the valance band edge of the semiconductor and less than the potential of the Fermi level of the semiconductor, the absolute value
  • the absolute value of the difference between the RHE potential and the potential of the conduction band edge being greater than zero and less than or equal to 0.2V.
  • the semiconductor may primarily comprise silicon, the catalyst layer may primarily comprise iron oxide, and the thickness of the catalyst layer may be less than 12 nm; (2) at least a portion of the semiconductor may comprise an array of nanowires or nanotubes covered at least in part by the catalyst layer; (3) the photoelectrode may be a photoanode, the interior of the semiconductor may be doped with an n-type dopant, and an exterior region of the semiconductor that is not covered by the catalyst layer may be doped with an n+ dopant; and (4) the photoelectrode may be a photocathode, the interior of the semiconductor may be doped with a p-type dopant, and an exterior region of the semiconductor that is not covered by the catalyst layer may be doped with a p+ dopant.
  • This invention may be implemented as a method of using a photoelectrochemical cell to generate electricity, which method comprises, in combination: (a) using a semiconductor in a photoelectrode to generate photocarriers, and (b) using a catalyst layer in the photoelectrode to alter the rate of an
  • the photoelectrode is a component of the photoelectrochemical cell
  • the semiconductor primarily comprises a first material and the catalyst layer primarily comprises a second material, the first material being different than the second material
  • the catalyst layer covers a portion of the semiconductor's surface and is positioned between the semiconductor and the electrolyte
  • the thickness of the catalyst layer is less than 60% of the minority carrier diffusion distance of the catalyst layer
  • the photoelectrode is either a photoanode or a photocathode
  • the photoanode has an OEP that is more than the potential of the valance band edge of the semiconductor and less than the potential of the Fermi level of the semiconductor, the absolute value of the difference between the OEP and the potential of the valence band edge being greater than zero and less than or equal to 0.2V
  • the semiconductor may comprise silicon and the catalyst layer may comprise iron oxide; (2) the catalyst layer may comprise iron oxide and the thickness of the layer may be less than 12 nm; (3) at least a portion of the semiconductor may comprise an array of nanowires or nanotubes covered at least in part by the catalyst layer; and (4) either (A) the photoelectrode may be a photoanode, the interior of the semiconductor may be doped with an n-type dopant, and an exterior region of the semiconductor that is not covered by the catalyst layer may be doped with an n+ dopant, or (B) the photoelectrode may be a photocathode, the interior of the semiconductor may be doped with a p-type dopant, and an exterior region of the semiconductor that is not covered by the catalyst layer may be doped with a p+ dopant.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Hybrid Cells (AREA)

Abstract

Selon des modes de réalisation donnés à titre d'exemples de la présente invention, une photoélectrode comprend un semi-conducteur pour une génération de porteurs de photons, et une couche de catalyseur destinée à modifier la vitesse de réaction dans un électrolyte adjacent. La couche de catalyseur recouvre une partie du semi-conducteur. L'épaisseur de la couche de catalyseur est inférieure à 60 % de sa distance de diffusion de porteurs de minorité. Si la photoélectrode est une photoanode, elle présente un potentiel effectif optimisé (OEP) qui est supérieur au potentiel du bord de la bande de valence mais inférieur au potentiel du niveau de Fermi du semi-conducteur. Si c'est une photocathode, elle présente un potentiel RHE qui est inférieur au potentiel du bord de la bande de conduction mais supérieur au potentiel du niveau de Fermi du semi-conducteur. La valeur absolue de la différence (OEP moins potentiel du bord de la bande de valence, ou potentiel RHE moins potentiel du bord de la bande de conduction) est supérieure à zéro et inférieure ou égale à 0,2 V.
PCT/US2012/045988 2011-07-07 2012-07-09 Procédés et appareil pour former une couche de catalyseur ultramince pour photoélectrode WO2013006867A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161505197P 2011-07-07 2011-07-07
US61/505,197 2011-07-07

Publications (1)

Publication Number Publication Date
WO2013006867A1 true WO2013006867A1 (fr) 2013-01-10

Family

ID=47437493

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/045988 WO2013006867A1 (fr) 2011-07-07 2012-07-09 Procédés et appareil pour former une couche de catalyseur ultramince pour photoélectrode

Country Status (2)

Country Link
US (1) US9920438B2 (fr)
WO (1) WO2013006867A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9478402B2 (en) 2013-04-01 2016-10-25 Kla-Tencor Corporation Photomultiplier tube, image sensor, and an inspection system using a PMT or image sensor
WO2016187603A1 (fr) * 2015-05-21 2016-11-24 Kla-Tencor Corporation Photocathode incluant un réseau d'émetteurs de champ sur un substrat de silicium comportant une couche de bore
US9529182B2 (en) 2013-02-13 2016-12-27 KLA—Tencor Corporation 193nm laser and inspection system
WO2017019846A1 (fr) 2015-07-30 2017-02-02 Macrogenics, Inc. Molécules se liant à pd-1 et méthodes d'utilisation correspondantes
US9601299B2 (en) 2012-08-03 2017-03-21 Kla-Tencor Corporation Photocathode including silicon substrate with boron layer
US9608399B2 (en) 2013-03-18 2017-03-28 Kla-Tencor Corporation 193 nm laser and an inspection system using a 193 nm laser
WO2017106061A1 (fr) 2015-12-14 2017-06-22 Macrogenics, Inc. Molécules bispécifiques présentant une immunoréactivité par rapport à pd-1 et à ctla-4 et leurs procédés d'utilisation
WO2017142928A1 (fr) 2016-02-17 2017-08-24 Macrogenics, Inc. Molécules de liaison de ror1, et procédés d'utilisation de celles-ci
US9748729B2 (en) 2014-10-03 2017-08-29 Kla-Tencor Corporation 183NM laser and inspection system
WO2017180813A1 (fr) 2016-04-15 2017-10-19 Macrogenics, Inc. Nouvelles molécules de liaison à b7-h3, leurs conjugués anticorps-médicaments et leurs procédés d'utilisation
US9804101B2 (en) 2014-03-20 2017-10-31 Kla-Tencor Corporation System and method for reducing the bandwidth of a laser and an inspection system and method using a laser
US9818887B2 (en) 2012-04-10 2017-11-14 Kla-Tencor Corporation Back-illuminated sensor with boron layer
WO2018119166A1 (fr) 2016-12-23 2018-06-28 Macrogenics, Inc. Molécules de liaison à adam9 et leurs procédés d'utilisation
US10175555B2 (en) 2017-01-03 2019-01-08 KLA—Tencor Corporation 183 nm CW laser and inspection system
US10943760B2 (en) 2018-10-12 2021-03-09 Kla Corporation Electron gun and electron microscope
US11072653B2 (en) 2015-06-08 2021-07-27 Macrogenics, Inc. LAG-3-binding molecules and methods of use thereof
US11114491B2 (en) 2018-12-12 2021-09-07 Kla Corporation Back-illuminated sensor and a method of manufacturing a sensor
US11114489B2 (en) 2018-06-18 2021-09-07 Kla-Tencor Corporation Back-illuminated sensor and a method of manufacturing a sensor
US11174315B2 (en) 2015-10-08 2021-11-16 Macrogenics, Inc. Combination therapy for the treatment of cancer
US11685781B2 (en) 2018-02-15 2023-06-27 Macrogenics, Inc. Variant CD3-binding domains and their use in combination therapies for the treatment of disease
US11795226B2 (en) 2017-12-12 2023-10-24 Macrogenics, Inc. Bispecific CD16-binding molecules and their use in the treatment of disease
US11848350B2 (en) 2020-04-08 2023-12-19 Kla Corporation Back-illuminated sensor and a method of manufacturing a sensor using a silicon on insulator wafer

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10208384B2 (en) * 2011-08-11 2019-02-19 Toyota Motor Engineering & Manufacturing North America, Inc. Efficient water oxidation catalysts and methods of oxygen and hydrogen production by photoelectrolysis
JP5982399B2 (ja) * 2011-12-06 2016-08-31 株式会社バイオフォトケモニクス研究所 バイオマス・有機・無機物の高効率分解浄化及び同時発電と水素生産の方法とそのためのバイオマス・有機・無機物直接燃料電池
WO2014037790A1 (fr) * 2012-09-05 2014-03-13 Zinniatek Limited Dispositifs photovoltaïques à éléments de surface tridimensionnels et leurs procédés de fabrication
JP2015200016A (ja) * 2014-03-31 2015-11-12 富士フイルム株式会社 水分解用光電極、水分解装置
US10745815B2 (en) * 2015-01-05 2020-08-18 Technion Research & Development Foundation Limited Non-uniform doping of photoelectrochemical cell electrodes
CN105742506B (zh) * 2016-02-29 2019-01-01 苏州大学 一种有机-无机杂化光电化学阳极电极及其制备方法
JP6770229B2 (ja) * 2016-08-31 2020-10-14 富士通株式会社 光化学電極及び酸素発生装置
CN114522339A (zh) * 2022-02-23 2022-05-24 清华大学 一种面向神经调控的薄膜光电极及其制备方法和应用
CN115896812A (zh) * 2022-11-29 2023-04-04 电子科技大学长三角研究院(湖州) 一种基于空心砖硒化亚锗薄膜的光解水产氧光阳极及其电极系统

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656103A (en) * 1983-02-18 1987-04-07 Energy Conversion Devices, Inc. Liquid junction photoelectrodes using amorphous silicon-based thin film semiconductor
US7122873B2 (en) * 2002-08-26 2006-10-17 University Of Hawaii Hybrid solid state/electrochemical photoelectrode for hyrodrogen production
US20070196268A1 (en) * 2006-02-22 2007-08-23 Smith John R Thermal activation of photocatalytic generation of hydrogen
US20070235711A1 (en) * 2006-03-31 2007-10-11 Intematix Corporation Methods of reducing the bandgap energy of a metal oxide
US20080286643A1 (en) * 2004-05-31 2008-11-20 Nissan Motor Co., Ltd. Photoelectrochemical Cell
US20100133110A1 (en) * 2008-10-08 2010-06-03 Massachusetts Institute Of Technology Catalytic materials, photoanodes, and photoelectrochemical cells for water electrolysis and other, electrochemical techniques
US20100282601A1 (en) * 2008-10-30 2010-11-11 Panasonic Corporation Photoelectrochemical cell and energy system using the same
US20110005590A1 (en) * 2009-07-09 2011-01-13 Rosestreet Labs Energy, Inc. Tandem Photoelectrochemical Cell for Water Dissociation

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4592807A (en) * 1983-05-19 1986-06-03 Union Oil Company Of California Methods of making highly conductive photoelectrochemical electrodes
US20120216854A1 (en) * 2011-02-25 2012-08-30 Chidsey Christopher E D Surface-Passivated Regenerative Photovoltaic and Hybrid Regenerative Photovoltaic/Photosynthetic Electrochemical Cell

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656103A (en) * 1983-02-18 1987-04-07 Energy Conversion Devices, Inc. Liquid junction photoelectrodes using amorphous silicon-based thin film semiconductor
US7122873B2 (en) * 2002-08-26 2006-10-17 University Of Hawaii Hybrid solid state/electrochemical photoelectrode for hyrodrogen production
US20080286643A1 (en) * 2004-05-31 2008-11-20 Nissan Motor Co., Ltd. Photoelectrochemical Cell
US20070196268A1 (en) * 2006-02-22 2007-08-23 Smith John R Thermal activation of photocatalytic generation of hydrogen
US20070235711A1 (en) * 2006-03-31 2007-10-11 Intematix Corporation Methods of reducing the bandgap energy of a metal oxide
US20100133110A1 (en) * 2008-10-08 2010-06-03 Massachusetts Institute Of Technology Catalytic materials, photoanodes, and photoelectrochemical cells for water electrolysis and other, electrochemical techniques
US20100282601A1 (en) * 2008-10-30 2010-11-11 Panasonic Corporation Photoelectrochemical cell and energy system using the same
US20110005590A1 (en) * 2009-07-09 2011-01-13 Rosestreet Labs Energy, Inc. Tandem Photoelectrochemical Cell for Water Dissociation

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9818887B2 (en) 2012-04-10 2017-11-14 Kla-Tencor Corporation Back-illuminated sensor with boron layer
US10446696B2 (en) 2012-04-10 2019-10-15 Kla-Tencor Corporation Back-illuminated sensor with boron layer
US10121914B2 (en) 2012-04-10 2018-11-06 Kla-Tencor Corporation Back-illuminated sensor with boron layer
US11081310B2 (en) 2012-08-03 2021-08-03 Kla-Tencor Corporation Photocathode including silicon substrate with boron layer
US9601299B2 (en) 2012-08-03 2017-03-21 Kla-Tencor Corporation Photocathode including silicon substrate with boron layer
US10199197B2 (en) 2012-08-03 2019-02-05 Kla-Tencor Corporation Photocathode including silicon substrate with boron layer
US9529182B2 (en) 2013-02-13 2016-12-27 KLA—Tencor Corporation 193nm laser and inspection system
US10439355B2 (en) 2013-02-13 2019-10-08 Kla-Tencor Corporation 193nm laser and inspection system
US9935421B2 (en) 2013-02-13 2018-04-03 Kla-Tencor Corporation 193nm laser and inspection system
US9608399B2 (en) 2013-03-18 2017-03-28 Kla-Tencor Corporation 193 nm laser and an inspection system using a 193 nm laser
US9478402B2 (en) 2013-04-01 2016-10-25 Kla-Tencor Corporation Photomultiplier tube, image sensor, and an inspection system using a PMT or image sensor
US9804101B2 (en) 2014-03-20 2017-10-31 Kla-Tencor Corporation System and method for reducing the bandwidth of a laser and an inspection system and method using a laser
US10495582B2 (en) 2014-03-20 2019-12-03 Kla-Tencor Corporation System and method for reducing the bandwidth of a laser and an inspection system and method using a laser
US9748729B2 (en) 2014-10-03 2017-08-29 Kla-Tencor Corporation 183NM laser and inspection system
US10199149B2 (en) 2014-10-03 2019-02-05 Kla-Tencor Corporation 183NM laser and inspection system
WO2016187603A1 (fr) * 2015-05-21 2016-11-24 Kla-Tencor Corporation Photocathode incluant un réseau d'émetteurs de champ sur un substrat de silicium comportant une couche de bore
US10748730B2 (en) 2015-05-21 2020-08-18 Kla-Tencor Corporation Photocathode including field emitter array on a silicon substrate with boron layer
EP4303235A2 (fr) 2015-06-08 2024-01-10 MacroGenics, Inc. Molecules de liaison lag-3 et leurs procedes d'utilisation
US11858991B2 (en) 2015-06-08 2024-01-02 Macrogenics, Inc. LAG-3-binding molecules and methods of use thereof
US11072653B2 (en) 2015-06-08 2021-07-27 Macrogenics, Inc. LAG-3-binding molecules and methods of use thereof
EP3456346A1 (fr) 2015-07-30 2019-03-20 MacroGenics, Inc. Molécules de liaison pd-1 et lag-3 et leurs procédés d'utilisation
WO2017019846A1 (fr) 2015-07-30 2017-02-02 Macrogenics, Inc. Molécules se liant à pd-1 et méthodes d'utilisation correspondantes
US10577422B2 (en) 2015-07-30 2020-03-03 Macrogenics, Inc. PD-1-binding molecules and methods of use thereof
EP3981792A1 (fr) 2015-07-30 2022-04-13 MacroGenics, Inc. Molécules de liaison pd-1 et leurs procédés d'utilisation
US11623959B2 (en) 2015-07-30 2023-04-11 Macrogenics, Inc. PD-1-binding molecules and methods of use thereof
US11174315B2 (en) 2015-10-08 2021-11-16 Macrogenics, Inc. Combination therapy for the treatment of cancer
US10954301B2 (en) 2015-12-14 2021-03-23 Macrogenics, Inc. Bispecific molecules having immunoreactivity with PD-1 and CTLA-4, and methods of use thereof
US11840571B2 (en) 2015-12-14 2023-12-12 Macrogenics, Inc. Methods of using bispecific molecules having immunoreactivity with PD-1 and CTLA-4
WO2017106061A1 (fr) 2015-12-14 2017-06-22 Macrogenics, Inc. Molécules bispécifiques présentant une immunoréactivité par rapport à pd-1 et à ctla-4 et leurs procédés d'utilisation
WO2017142928A1 (fr) 2016-02-17 2017-08-24 Macrogenics, Inc. Molécules de liaison de ror1, et procédés d'utilisation de celles-ci
WO2017180813A1 (fr) 2016-04-15 2017-10-19 Macrogenics, Inc. Nouvelles molécules de liaison à b7-h3, leurs conjugués anticorps-médicaments et leurs procédés d'utilisation
US11591400B2 (en) 2016-04-15 2023-02-28 Macrogenics, Inc. B7-H3 directed antibody drug conjugates
US10961311B2 (en) 2016-04-15 2021-03-30 Macrogenics, Inc. B7-H3 binding molecules, antibody drug conjugates thereof and methods of use thereof
WO2018119166A1 (fr) 2016-12-23 2018-06-28 Macrogenics, Inc. Molécules de liaison à adam9 et leurs procédés d'utilisation
US10175555B2 (en) 2017-01-03 2019-01-08 KLA—Tencor Corporation 183 nm CW laser and inspection system
US10429719B2 (en) 2017-01-03 2019-10-01 Kla-Tencor Corporation 183 nm CW laser and inspection system
US11795226B2 (en) 2017-12-12 2023-10-24 Macrogenics, Inc. Bispecific CD16-binding molecules and their use in the treatment of disease
US11685781B2 (en) 2018-02-15 2023-06-27 Macrogenics, Inc. Variant CD3-binding domains and their use in combination therapies for the treatment of disease
US11114489B2 (en) 2018-06-18 2021-09-07 Kla-Tencor Corporation Back-illuminated sensor and a method of manufacturing a sensor
US10943760B2 (en) 2018-10-12 2021-03-09 Kla Corporation Electron gun and electron microscope
US11114491B2 (en) 2018-12-12 2021-09-07 Kla Corporation Back-illuminated sensor and a method of manufacturing a sensor
US11848350B2 (en) 2020-04-08 2023-12-19 Kla Corporation Back-illuminated sensor and a method of manufacturing a sensor using a silicon on insulator wafer

Also Published As

Publication number Publication date
US9920438B2 (en) 2018-03-20
US20130008495A1 (en) 2013-01-10

Similar Documents

Publication Publication Date Title
US9920438B2 (en) Methods and apparatus for ultrathin catalyst layer for photoelectrode
Ahmet et al. Demonstration of a 50 cm 2 BiVO 4 tandem photoelectrochemical-photovoltaic water splitting device
Wen et al. Nanoengineering energy conversion and storage devices via atomic layer deposition
Young et al. Photo-assisted water oxidation with cobalt-based catalyst formed from thin-film cobalt metal on silicon photoanodes
Mei et al. Crystalline TiO2: a generic and effective electron-conducting protection layer for photoanodes and-cathodes
Li et al. Prototype of a scalable core–shell Cu2O/TiO2 solar cell
Zhao et al. Oxidatively stable nanoporous silicon photocathodes with enhanced onset voltage for photoelectrochemical proton reduction
Tawfik et al. Highly conversion efficiency of solar water splitting over p-Cu2O/ZnO photocatalyst grown on a metallic substrate
Cox et al. Interfaces between water splitting catalysts and buried silicon junctions
US8221599B2 (en) Corrosion-resistant anodes, devices including the anodes, and methods of using the anodes
Park et al. Photoelectrochemical oxygen evolution improved by a thin Al2O3 interlayer in a NiOx/n-Si photoanode
Hong et al. Effect of oxygen evolution catalysts on hematite nanorods for solar water oxidation
CN103682153B (zh) 用于钙钛矿型有机卤化铅薄膜太阳能电池的金属‑绝缘层‑半导体背接触界面结构及其制备方法
Yin et al. 11.5% efficiency of TiO 2 protected and Pt catalyzed n+ np+-Si photocathodes for photoelectrochemical water splitting: manipulating the Pt distribution and Pt/Si contact
CN102206801B (zh) 基于碲化镉的薄膜光伏器件所用的导电透明氧化物膜层的形成方法
Sun et al. Metal on metal oxide nanowire Co-catalyzed Si photocathode for solar water splitting
US20110139247A1 (en) Graded alloy telluride layer in cadmium telluride thin film photovoltaic devices and methods of manufacturing the same
Li et al. Simultaneous enhancement of photovoltage and charge transfer in Cu2O-based photocathode using buffer and protective layers
Li et al. Efficient photoelectrochemical water oxidation enabled by an amorphous metal oxide-catalyzed graphene/silicon heterojunction photoanode
Ku et al. Creation of 3D Textured Graphene/Si Schottky Junction Photocathode for Enhanced Photo‐Electrochemical Efficiency and Stability
US20120024380A1 (en) Intermixing of cadmium sulfide layers and cadmium telluride layers for thin film photovoltaic devices and methods of their manufacture
US20140000713A1 (en) Mechanically stable device based on nano/micro wires and having improved optical properties and process for producing it
Moreno-Hernandez et al. Conformal SnO x heterojunction coatings for stabilized photoelectrochemical water oxidation using arrays of silicon microcones
Zhao et al. InGaN/Cu2O heterostructure core-shell nanowire photoanode for efficient solar water splitting
WO2014134515A1 (fr) Cellules solaires à hétérojonction d'oxyde de zinc et de silicium à haute efficacité et à faible coût

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12806971

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12806971

Country of ref document: EP

Kind code of ref document: A1